Patent GB-1080564-A (GB)
Title: Improvements in and relating to polyurethane elastomers
IPC: C08G18/10
Filed: 1964-06-23
Abstract: Elastic films and fibres of a polymer containing the repeating unit <FORM:1080564/C3/1> wherein R and R1 are divalent organic groups, n is an integer of at least 1; m is 0 or 1; each X is -O-or-NR7-where R7 is a hydrogen atom or alkyl group, or where both X variables are -NR7, the two R7 radicals taken together form an alkylene radical which together with the two N atoms and R1 complete a heterocyclic ring; p is 0 or 1, provided that when p is 0, X is -NR7-; q is an integer of value at least 1; and L is a divalent organic group derived from a hydroxyl terminated organic polymer HO-L-OH of M.W. at least 700, hydroxyl number less than 170, melting point less than 75 DEG  C. and containing at least 50 mole per cent of carbonylpentamethyleneoxy units, are prepared by (i) preparing a prepolymer by reacting an excess of an organic diisocyanate with the polymer HO-L-OH, (ii) reacting the prepolymer preferably in solution, e.g. in dimethyl sulphoxide, N,N-dimethylformamide or N,N-dimethylacetamide, with a curing compound, e.g. glycol, diamine or amino alcohol having two active hydrogen-containing groups and casting or spinning a solution of the elastomer, e.g. into a water bath.  The films or fibres may be post-cured if desired.  The group L in the polymer OH-L-OH consists substantially wholly of carbonylpentamethyleneoxy units together with units of at least one group selected from <FORM:1080564/C3/2> in which R2 is an organic group; <FORM:1080564/C3/3> in which r is 2 to 10, and R3 is H, alkyl, alkoxy, haloalkyl, alkoxyalkyl, or halo derivatives thereof, and at least one of the R3 radicals is other than H; <FORM:1080564/C3/4> in which R4 is hydrocarbyl, hydrocarbyloxymethyl, acyloxymethyl, nitro, dihydrocarbylamino, cyanoalkyl, or cyanoalkoxymethyl; and -OCHR5CHR6- in which R5 is H or methyl and R6 is methyl or ethyl.  The polymer HO-L-OH may be prepared by reacting a bifunctional initiator with (1) epsilon-caprolactone to produce a hydroxylterminated polymer a stoiochiometric excess of which is then reacted with an organic diisocyanate, (2) with a mixture of epsilon-caprolactone and a suitably substituted lactone preferably in presence of a catalyst, (3) with a mixture of epsilon-caprolactone and one or more cyclic carbonates preferably in presence of a catalyst, (4) with a mixture of epsilon caprolactone and an alkylene oxide.  Any or all of the four embodiments of L can be combined in a single polymer HO-L-OH. Preferably the hydroxyl-terminated polymer will contain at least 5 mol per cent of a divalent organic group which contains a pendant substituent non-reactive with isocyanate, or which is unsymmetrical or both.  Preferably also the polymer has a Poisson molecular weight distribution.  The storage life of solutions of prepolymer and curing agent may be lengthened by addition of small quantities of acid.  In Exs. 1, 3, epsilon caprolactone was polymerized, using diethylene glycol as initiator and tetraisopropyl titanate as catalyst, and extended with a mixture of 2, 4 and 2, 6 tolylene diisocyanate.  The resulting diol was sapped with bis(4-isocyanatophenyl)methane, dissolved in N,N-dimethylformamide and the solution stabilized with phosphoric acid.  Ethylene diamine was added as curing agent to form a spinning solution for elastic fibres.  In Ex. 2 the initiator was ethylene glycol.  Exs. 5, 9 use a polymeric diol from epsilon-caprolactone and methyl-epsilon-caprolactone, with diethylene glycol and stannous octoate as catalyst, and in Ex. 9 p-xylylene diisocyanate is used to form the prepolymer.  Ex. 10 uses as polymeric diol, a copolymer of epsilon-caprolactone and 4,4 - dimethyl - 2,6 - dioxacyclohexanone prepared with diethylene glycol as initiator and tetraisopropyl titanate as catalyst.  Reference has been directed by the Comptroller to the Specification 887,180.